CN108821327A - 一种类松果状的ZnO纳米微球的制备方法、及其应用 - Google Patents
一种类松果状的ZnO纳米微球的制备方法、及其应用 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 179
- 239000011787 zinc oxide Substances 0.000 claims abstract description 89
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 13
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- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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Abstract
本发明提供一种类松果状的ZnO纳米微球的制备方法、及其应用,包括以下步骤:1)、利用醋酸锌、造孔剂、掺杂剂制备前驱体混合溶液;2)、利用前驱体混合溶液制备前驱体薄膜;3)、通过控制不同是升温速率制备类松果状ZnO纳米微球;本发明制备设备成熟,工艺简单,方便规模化生产;本发明通过准确控制制备的过程中不同反应温度,以及利用醋酸锌、造孔剂分解成水和二氧化碳,从微球中分离出来,帮助形成孔道,通过利用掺杂剂为氯化锂(LiCl)中Cl离子以气体的形式分离出来,帮助形成更多的孔道,制备的微球的尺寸可控,孔道分布均匀;本发明制备类松果状的Li掺杂ZnO纳米微球适用范围广,可应用于催化降解、光电探测器、气敏探测器等领域发挥积极作用。
Description
技术领域
本发明涉及一种ZnO纳米技术领域,尤其是一种类松果状的ZnO纳米微球的制备方法、及其应用。
背景技术
氧化锌(ZnO)是一种典型的第三代半导体材料。由于ZnO晶体在室温下带隙宽度高达3.37eV,激子束缚能高达60meV,在紫外波段具有强的自由激子跃迁发光,且具有化学稳定性、近紫外发射、生物无毒性等特性,使其在光催化、光电、光伏和传感器等领域中具有独特的优越性和潜在的应用前景。
ZnO材料一个非常重要的研究方向就是ZnO纳米材料,例如ZnO纳米点、ZnO纳米球、ZnO纳米柱、ZnO纳米花等等。ZnO纳米材料具有很大的比表面积、量子效应、局域表面限制效应等突出的优点,因此,ZnO纳米材料一直是一个研究的热点。
在催化和气敏传感当中,大的比表面积可以有效提高催化和检测效率。对于ZnO纳米球而言,如果可以进一步增大其比表面积,有助于更好的发挥其突出的催化和气敏传感特性。
纳米ZnO晶体作为染料敏化电池(DSC S)电极材料的报道在近年来激增。然而,如何提高ZnO电极的最高光电转化率(PCE),一直是科研工作者的研究重点。其中,通过制备不同微观几何形状的纳米ZnO晶体作为电极材料,是研究提高PCE值的主要策略。同时,若纳米ZnO结构单元晶体进一步自组装以制备多级结构的ZnO晶体,其宏观结构尺度与光波长相近,将对光波具有很强的散射能力,从而可提高光电子的捕获量;并且其微观结构纳米尺度的ZnO晶体又增加了对染料的附着面积,因此这种多级结构的ZnO晶体将具有较高的PCE值。例如,Ko等(Nano Letters,11,666,2011)将在掺氟导电玻璃(FTO)基片上,通过水热法是ZnO纳米线重复多次在相互垂直的两个方向上附着的ZnO量子点种子上生长,制备出了类似于树木的多级结构ZnO纳米线,并检测得到其最高染料敏化光电转化效率为2.63%,这比一级结构的ZnO纳米线的光电转化效率高出了五倍。Zhang等(Angew.Chem.Int.Ed.,120,2436,2008)将锌盐在多元醇介质中高温水解,制得了由纳米ZnO颗粒自主装而成的亚微米尺度的多级结构ZnO微球;他们将该ZnO微球涂覆在FTO基片上,然后负载染料制得光电转化电极,测得了该电极的最大PEC值为5.4%。Saito等(Energ.Environ.Sci.,1,280,2008)将直径为20nm的商用纳米ZnO颗粒分散在乙醇/水/醋酸的混合溶剂中,并将其刮涂在FTO基片上制得由纳米ZnO颗粒堆砌而成的具有多级结构的ZnO薄膜,该ZnO电极的最大PEC值经测定达6.58%。Memarin等(Angew.Chem.Int.Ed.,50,12321,2011)对Saito等的工作做了改进,他们首先通过喷雾热解法在FTO表面形成一层致密ZnO薄膜,然后再采用Saito等的方法将直径为20nm的商用纳米ZnO颗粒刮涂在致密ZnO薄膜上,制得由纳米ZnO颗粒堆砌成的ZnO亚微米微球层和致密ZnO薄膜层的电极,该电极的最高PEC值达到了7.5%。
这种具有纳米微结构和微米宏观结构的多级结构ZnO晶体,具有优异的光电性能,然而其制备方法却较为复杂,通过简单方法一步制备出具有上述多级结构ZnO晶体的文献报道较少。最近,Liu等(Chem.Mater.,19,5824,2007)采用三甲基溴化铵(CTAB)作为保护剂、硝酸锌为锌源,通过水热法制备出了由花朵形ZnO结构单元构建的中空ZnO微球。但是,该方法合成的多级结构ZnO微球尺寸度在20μm左右,其次ZnO结构单元在500nm左右。由于该微球尺度过大将对光的散射效果不会很好,同时其次级结构尺度也较大从而对染料的附着量也不会很高,可以预想由其制备的电极材料将不会有较高的PEC值。Zhang等(Ind.Eng.Chem.Res.,50,13355,2011)利用微型多孔膜分离设备,制备了尺度在10μm左右的由片层纳米ZnO颗粒自组装而成的ZnO微球,也存在多级结构,但是其宏观尺寸过大、且制备工艺复杂,用于光电转化电极材料优势不明显。
发明内容
针对现有技术的不足,本发明提供一种类松果状的ZnO纳米微球制备方法、及其应用,本发明制备的ZnO纳米微球的尺寸可控,分布均与性好。
本发明的技术方案为:
一种类松果状的ZnO纳米微球的制备方法,包括以下步骤:
1)、前驱体混合溶液的制备,将造孔剂、掺杂剂、醋酸锌按照质量比为0.5-2:10-50:100的比例加入到溶剂中,在60-100℃下磁力搅拌60-120min,得到澄清的前驱体混合溶液;
2)、前驱体薄膜的制备,将基板放置在加热电板上,并加热到100-250℃,使用喷枪,将步骤1)制备好的前驱体混合溶液以喷雾的形式均匀喷到基板上,乙二醇迅速挥发,基板上只保留下前驱体薄膜;
3)、类松果状ZnO纳米微球的制备,将步骤2)制备的前驱体薄膜为转移到箱式退火炉中,从室温开始,以1℃/min的速率升温至100℃,保温60-120min,然后以1℃/min的速率升温至350℃,保温30-60min;接着,以1℃/min的速率升温至500℃,保温30-120min,之后自然冷却至室温,得到类松果状ZnO纳米微球。
进一步的,步骤1)中造孔剂为聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物,掺杂剂为氯化锂(LiCl),溶剂为乙二醇。
进一步的,步骤2)中,喷枪的压强为5MPa,喷雾20-240s。
进一步的,步骤3)中,在350℃保温阶段,造孔剂聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物逐步团聚,从而形成纳米微孔,在350℃升温至500℃过程中,醋酸锌、造孔剂聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物分解成水和二氧化碳,从微球中分离出来,帮助形成孔道,同时,掺杂剂为氯化锂(LiCl)中Cl离子会以气体的形式分离出来,帮助形成更多的孔道;在500℃保温阶段,前驱体会完全分解掉,并促进微球结晶,从而获得结晶状态良好的类松果状的Li掺杂ZnO纳米微球。
本发明还提供一种类松果状ZnO纳米微球的应用,该类松果状ZnO纳米微球可应用于催化降解、光电探测器、气敏探测器。
本发明的有益效果为:
1、本发明制备设备成熟,工艺简单,方便规模化生产;
2、本发明通过准确控制制备的过程中不同反应温度,以及利用醋酸锌、造孔剂分解成水和二氧化碳,从微球中分离出来,帮助形成孔道,同时,通过利用掺杂剂为氯化锂(LiCl)中Cl离子会以气体的形式分离出来,帮助形成更多的孔道,制备的微球的尺寸可控,孔道分布均匀;
3、本发明制备类松果状的Li掺杂ZnO纳米微球适用范围广,可应用于催化降解、光电探测器、气敏探测器等领域发挥积极作用。
附图说明
图1为本发明实施例1制备的类松果状的Li掺杂ZnO纳米微球的SEM图;
图2为本发明实施例1制备的类松果状的Li掺杂ZnO纳米微球的X射线衍射图谱(XRD);
图3为本发明实施例1制备的类松果状的Li掺杂ZnO纳米微球的催化降解亚甲基蓝的吸收光谱图;
图4为本发明实施例3类松果状的Li掺杂ZnO纳米微球的光电探测器结构的示意图;
图5为本发明实施例4类松果状的Li掺杂ZnO纳米微球的气敏探测器的结构示意图。
具体实施方式
下面结合附图对本发明的具体实施方式作进一步说明:
实施例1
一种类松果状的ZnO纳米微球的制备方法,包括以下步骤:
1)、前驱体混合溶液的制备,将聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物、氯化锂(LiCl)、醋酸锌按照质量比为0.5:20:100的比例加入到10mL乙二醇中,在60℃下磁力搅拌60min,得到澄清的前驱体混合溶液;
2)、前驱体薄膜的制备,将基板放置在加热电板上,并加热到200℃,使用喷枪,将步骤1)制备好的前驱体混合溶液以喷雾的形式均匀喷到基板上,乙二醇迅速挥发,基板上只保留下前驱体薄膜,其中,喷枪的压强为5MPa,喷雾30s;
3)、类松果状ZnO纳米微球的制备,将步骤2)制备的前驱体薄膜为转移到箱式退火炉中,从室温开始,以1℃/min的速率升温至100℃,保温60min,然后以1℃/min的速率升温至350℃,保温30min;接着,以1℃/min的速率升温至500℃,保温30min,之后自然冷却至室温,得到类松果状ZnO纳米微球。
在350℃保温阶段,聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物逐步团聚,从而形成纳米微孔,在350℃升温至500℃过程中,醋酸锌、造孔剂聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物分解成水和二氧化碳,从微球中分离出来,帮助形成孔道,同时,掺杂剂为氯化锂(LiCl)中Cl离子会以气体的形式分离出来,帮助形成更多的孔道;在500℃保温阶段,前驱体会完全分解掉,并促进微球结晶,从而获得结晶状态良好的类松果状的Li掺杂ZnO纳米微球,该微球的SEM图如图1所示,从图中可以看出,ZnO纳米微球分散较为均匀,且呈现类松果状;从图2中可以看出,尖锐的ZnO衍射峰说明Li掺杂ZnO纳米微球具有良好的结晶性能,从图3中可以看出,经0.5小时催化降解之后,亚甲基蓝的浓度大幅度降低,由此可以说明,Li掺杂ZnO纳米微球具有显著的光催化降解性能。
实施例2
一种类松果状的ZnO纳米微球的制备方法,包括以下步骤:
1)、前驱体混合溶液的制备,将聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物、氯化锂(LiCl)、醋酸锌按照质量比为0.5:25:100的比例加入到15mL乙二醇中,在80℃下磁力搅拌60min,得到澄清的前驱体混合溶液;
2)、前驱体薄膜的制备,将基板放置在加热电板上,并加热到200℃,使用喷枪,将步骤1)制备好的前驱体混合溶液以喷雾的形式均匀喷到基板上,乙二醇迅速挥发,基板上只保留下前驱体薄膜,其中,喷枪的压强为5MPa,喷雾60s;
3)、类松果状ZnO纳米微球的制备,将步骤2)制备的前驱体薄膜为转移到箱式退火炉中,从室温开始,以1℃/min的速率升温至100℃,保温80min,然后以1℃/min的速率升温至350℃,保温40min;接着,以1℃/min的速率升温至500℃,保温60min,之后自然冷却至室温,得到类松果状ZnO纳米微球;
在350℃保温阶段,聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物逐步团聚,从而形成纳米微孔,在350℃升温至500℃过程中,醋酸锌、造孔剂聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物分解成水和二氧化碳,从微球中分离出来,帮助形成孔道,同时,掺杂剂为氯化锂(LiCl)中Cl离子会以气体的形式分离出来,帮助形成更多的孔道;在500℃保温阶段,前驱体会完全分解掉,并促进微球结晶,从而获得结晶状态良好的类松果状的Li掺杂ZnO纳米微球。
实施例3
类松果状的Li掺杂ZnO纳米微球应用于光电探测器
在实施例1制备的类松果状的Li掺杂ZnO纳米微球上继续外延生长Au电极,从而制备得到光电探测器,具体为:使用掩膜板和电子束蒸发金属Au电极,经过退火处理形成欧姆接触和肖特基结,该光电探测器包括类松果状的Li掺杂ZnO纳米微球和金属Au电极,其结构如图4所示,所制备的类松果状的Li掺杂ZnO纳米微球光电探测器在1V偏压下,暗电流仅为31.2pA,并且器件在1V偏压下,最大值达到了0.89A/W。
实施例4
类松果状的Li掺杂ZnO纳米微球应用于气敏传感器
在实施例1制备的类松果状的Li掺杂ZnO纳米微球上继续外延生长Pt电极,从而制备成光电探测器,具体为:使用掩膜板和电子束蒸发金属Pt电极,经过退火处理形成欧姆接触和肖特基结,该光电探测器结构如图5所示,其探测精度高,对乙醇可达5ppm,相应时间为6s。
上述实施例和说明书中描述的只是说明本发明的原理和最佳实施例,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。
Claims (5)
1.一种类松果状的ZnO纳米微球的制备方法,其特征在于,包括以下步骤:
1)、前驱体混合溶液的制备,将造孔剂、掺杂剂、醋酸锌按照质量比为0.5-2:10-50:100的比例加入到溶剂中,在60-100℃下磁力搅拌60-120min,得到澄清的前驱体混合溶液;
2)、前驱体薄膜的制备,将基板放置在加热电板上,并加热到100-250℃,使用喷枪,将步骤1)制备好的前驱体混合溶液以喷雾的形式均匀喷到基板上,乙二醇迅速挥发,基板上只保留下前驱体薄膜;
3)、类松果状ZnO纳米微球的制备,将步骤2)制备的前驱体薄膜为转移到箱式退火炉中,从室温开始,以1℃/min的速率升温至100℃,保温60-120min,然后以1℃/min的速率升温至350℃,保温30-60min;接着,以1℃/min的速率升温至500℃,保温30-120min,之后自然冷却至室温,得到类松果状ZnO纳米微球。
2.根据权利要求1所述的一种类松果状的ZnO纳米微球的制备方法,其特征在于:步骤1)中,造孔剂为聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物,掺杂剂为氯化锂(LiCl),溶剂为乙二醇。
3.根据权利要求1所述的一种类松果状的ZnO纳米微球的制备方法,其特征在于:步骤2)中,喷枪的压强为5MPa,喷雾时间为20-240s。
4.根据权利要求1所述的一种类松果状的ZnO纳米微球的制备方法,其特征在于:步骤3)中,在350℃保温阶段,造孔剂聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物逐步团聚,从而形成纳米微孔,在350℃升温至500℃过程中,醋酸锌、造孔剂聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物分解成水和二氧化碳,从微球中分离出来,帮助形成孔道,同时,掺杂剂为氯化锂(LiCl)中Cl离子会以气体的形式分离出来,帮助形成更多的孔道;在500℃保温阶段,前驱体会完全分解掉,并促进微球结晶,从而获得结晶状态良好的类松果状的Li掺杂ZnO纳米微球。
5.根据权利要求1所述的一种类松果状的ZnO纳米微球的应用,其特征在于:该类松果状ZnO纳米微球可应用于催化降解、光电探测器、气敏探测器。
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